Continuous dyeing of synthetic fibers with water-immiscible organic solvents and amino hydroxy anthraquinones

ABSTRACT

IN WHICH X DENOTES OXYGEN OR SULPHUR AND R REPRESENTS A C4-C18-ALKYL RADICAL OR AN ALKOXYALKYL, CYCLOALKOXYALKYL, ARALKOXYALKYL OR ARYLOXYALKYL RADICAL, AND THAT THE MATERIALS ARE SUBSEQUENTLY SUBJECTED TO A HEAT TREATMENT THE DYEINGS OBTAINED ARE DISTINGUISHED BY HIGH DYESTUFF YIELD, VERY GOOD BUILD-UP AND EXCELLENT FASTNESS PROPERTIES, ESPECIALLY VERY GOOD FASTNESS TO THERMOFIXING, WASHING, RUBBING AND LIGHT.   1-NH2,4-HO,(R-X-)ANTHRAQUINONE   PROCESS FOR THE CONTINUOUS DYEING OF SYNTHETIC FIBRE MATERIALS FROM ORGAINC SOLVENTS, CHARACTERISED IN THAT THE FIBRE MATERIALS ARE IMPREGNATED WITH DYEING LIQUORS WHICH CONTAIN ANTHRAQUIONE DYESTUFFS OF FORMULA

United States Patent O 3,743,476 CONTINUOUS DYEING OF SYNTHETIC FIBERSWITH WATER-IMMISCIBLE ORGANIC SOL- VENTS AND AMINO HYDROXY ANTHRA-QUINONES Giinter Gehrke, Volker Hederich, and Peter Wagner,

Cologne, and Riitger Neelf, Leverkusen, Germany, assignors to BayerAktiengesellschaft, Leverkusen, Germany No Drawing. Filed Aug. 10, 1970,Ser. No. 62,652 Claims priority, application Germany, Aug. 16, 1969,

P 19 41 699.0 Int. Cl. C09b l/50; D06p 1/20 US. Cl. 8-39 13 ClaimsABSTRACT OF THE DISCLOSURE Process for the continuous dyeing ofsynthetic fibre materials from organic solvents, characterised in thatthe fibre materials are impregnated with dyeing liquors which containanthraquinone dyestuffs of formula NH, II I in which X denotes oxygen orsulphur and R represents a C -C -alkyl radical or an alkoxyalkyl,cycloalkoxyalkyl, aralkoxyalkyl or aryloxyalkyl radical, and that thematerials are subsequently subjected to a heat treatment.

The dyeings obtained are distinguished by high dyestufl? yield, verygood build-up and excellent fastness properties, especially very goodfastness to thermofixing, washing, rubbing and light.

The invention relates to a process for the continuous dyeing ofsynthetic fibre materials from organic solvents; the process ischaracterised in that the fibre materials are impregnated with dyeingliquors, which contain anthraquinone dyestuifs of formula X denotesoxygen or sulphur and R represents a C -C -alkyl, preferably C C -alkyl,or an alkoxyalkyl, cycloalkoxyalkyl, aralkoxyalkyl or aryloxyalkylradical,

- 3,743,476 Patented July 3, 197% As cycloalkoxyalkyl radicals, thecyclohexoxy-ethyL cyclohexoxy-propyl, methyl cyclohexoxy ethyl and.

methyl-cyclohexoxy-propyl radical. As aralkoxyalkyl radicals, thebenzyloxy-ethyl, benzyloxy-propyl, methyl-benzyloxy-ethyl,methoxy-benzyloxyethyl and 'benzyloxy-butyl radical.

As aryloxyalkyl radicals, the 3-methyl-2-iso-propylphenoxy-ethyl, isopropyl phenoxy-propyl, cyclohexylphenoxy-propyl,a,a-dimethyl-benzyl-phenoxy-propyl, p-

tert.-butyl-phenoxy iso propyl, cyclohexyl-phenoxy-isopropyl,phenoxy-iso-butyl, benzyl-phenoxy-iso-butyl, isopropyl-phenoxy-iso-butyland methyl phenoxy butyl radical.

Preferred anthraquinone dyestnfis of Formula I are those in which Rrepresents an alkoxyalkyl, cycloalkoxyalkyl, aralkoxyalkyl oraryloxyalkyl radical described by one of the three Formulae A, B and C;1

in which n is 1 or 2 and R represents a C -C -a1kyl, cycloalkyl, aralkylradical or a phenyl radical which is optionally substituted by C -C-alkyl, cycloalkyl, aralkyl, C -C -alkoxy, C -C alkylmercapto or C -C-alkoxycarb0nyl groups and/ or chlorine atoms, with the proviso that thesum of the carbon atoms contained in R is at least 2 and at most 18.

--oH-GHz-0R1 in which R represents a methyl or ethyl group, and

R has the significance given under Formula A, with the proviso that thesum of the carbon atoms contained in R is at least 2 and at most 18.

C -C -alkyl, cycloalkyl or aralkyl radical or a phenyl radical which isoptionally substituted by C -C -alkyl, cycloalkyl, aralkyl, C C -a1koxy,C -C -alkylmercapto or C -C -alkoxycarbonyl groups and/ or chlorineatoms, with the proviso that the sum of the carbon atoms contained intotal in R and R is at least 4 and at most 36.

For R the following may be mentioned as examples of C C preferably C -C-alkyl radicals: n-propyl, iso-propyl, n-butyl, tert.-butyl,2-ethyl-hexyl and the dodecyl radical.

As cycloalkyl radicals, the cyclohexyl and the methylcyclohexyl radicalmay be mentioned, and as aralkyl radicals, the benzyl radical andespecially the a,ot-dimethylbenzyl radical may be mentioned.

Possible optionally substituted phenyl radicals are for example: the4-methyl-, 2,4-dimethyl-, 4-ethyl-, 3- methyl-, 2-iso-propyl-,tert.-butyl-, iso-nonyl-, the cycloheXyl-, benzyl-, a-methylbenzyL,methoxy-, ethoxy-, methylmercaptoand butoxy-carbonyl-phenyl radical.

The dyestuffs used according to the invention for the dyeing fromorganic solvents are obtained according to processes which are inthemselves known, for example by reaction of1-amino-4-hydroxy-anthraquinones, which in the 2- or 3-position carry areplaceable substituent such as chlorine or bromine, lower alkoxy orphenoxy radicals or sulphonic acid groups, with hydroxyor mercaptoalkylcompounds which can be substituted by alkoxy or aryloxy groups, in thepresence of inorganic or organic bases, optionally using inert solventssuch as N-methylpy'rrolidone or dimethylformamide, or, for example, byreaction of appropriate 2- or 3-hydroxyor rnercapto-anthraquinones with,for example, aryl-sulphonyl-oxyalkyl compounds.

Possible organic solvents for the process according to the invention arethose solvents which are immiscible with water and of which the boilingpoints lie between 40 and 150 C., for example aromatic hydrocarbons,such as toluene or xylene, and aliphatic halogenated hydrocarbons,especially chloro-hydrocarbons, such as methylene chloride, chloroform,carbon tetrachloride, 1,1-clichlorethane, 1,2-dichlorethane,1,1,2-trichlorethane, 1,1, 1,2-tetrachlorethane, 1,1,2,2tetrachlorethane, pentachlorethane, l-chloropropane, 2-chloropropane,1,2-dichloropropane, 1,1,1-trichloropropane, l-chlorobutane,2-chlorobutane, 1,4-dichlorobutane, 1-chloro-2-methylpropane orZ-chloro-Z-methylpropane, as well as aliphatic fluoroorfluoro-chloro-hydrocarbons, such as perfiuoron-hexane,1,2,Z-trifiuoro-trichlorethane and 1,1,1-trifluoropentachloropropane,and aromatic chloroand fluoro-hydrocarbons, such as chlorobenzene,fluorobenzene, chlorotoluene and benzotrifluoride.

Tetrachlorethylene, trichlorethylene and 1,1,l-trichlorethane haveproved particularly suitable. Mixtures of these solvents can also beused.

The synthetic fibre materials to be dyed according to the process of theinvention are especially fibre materials of polyesters, for examplepolyethylene terephthalates or polyesters from1,4-bis-(hydroxymethyl)-cyclohexane and terephthalic acid, of cellulosetriacetate, of synthetic polyamides, such as poly-e-caprolactam,polyhexamethylenediamine adipate or poly-w-aminoundecane-acid, ofpolyurethanes or of polyolefins. The fibre materials can be. in the formof woven fabrics and knitted fabrics.

For the dyeing, the dyestuffs to be used according to the invention aredissolved in the water-immiscible organic solvents or added to these inthe form of solutions in solvents which are infinitely miscible withthese solvents, such as alcohols, dimethylformamide, dimethylacetamide,dimethylsulphoxide or sulpholane, and the synthetic fibre materials areimpregnated with the resulting clear dyestuff solutions, which canoptionally additionally contain soluble non-ionic auxiliary agents, forexample the known surface-active oxethylation and propoxylation productsof fatty alcohols, alkylphenols, fatty acid amides and fatty acids, forimproving the uniformity of the dyeings. Thereafetr the dyestuffs arefixed on the fibre materials by a heat treatment. The heat treatment canconsist of a brief dry heat treatment at 120230 C., with the dry heattreatment optionally being preceded by an intermediate drying, or of atreatment of the fibre materials in superheated solvent vapour atIOU-150 C. Small amounts of non-fixed dyestutf can be eluted by brieftreatment with the cold organic solvent. It should be pointed out thatmixtures of the dyestufis to be used according to the invention at timesgive a better colour yield than the individual dyestuffs and maysometimes show better solubility in the organic solvent.

Using the process according to the invention it is possible, when dyeingfrom organic solvents, to achieve dyeings on synthetic fibre materialswhich are distin guished by high dyestuif yield, very good build-up andexcellent fastness properties, especially very good fastness tothermofixing, washing, rubbing and light. A further advantage of thedyestuffs to be used according to the invention is their high solubilityin organic solvents, especially in tetrachlorethylene, trichlorethylene,1,1,1- trichlorethane and 1,1,l-trichloropropane, which make it possibleto carry out the dyeing even without the use of solubilising agents.

The parts indicated in the examples which follow are parts by weight.

EXAMPLE 1 A woven fabric of polyethylene terephthalate fibres isimpregnated at room temperature with a clear red solution which contains10 parts of 1-amino-2-(n-hexadecanoxy)-4-hydroxy-anthraquinone in 990parts of tetrachlorethylene. After squeezing out to a weight increase of60%, the woven fabric is dried for one minute at C.

Thereafter the dyestuff is fixed by heating the woven fabric to 190220C. for 45 seconds. Thereafter the small amount of non-fixed dyestulf iseluted by brief treatment in cold tetrachlorethylene for 20 seconds.After drying, a clear red dyeing is Obtained which is distinguished byits high dyestutf yield, very good build-up as well as good fastnessproperties, especially good fastness to thermofixing, washing, rubbingand light.

Equivalent red dyeings were also obtained analogously on woven fabricsof (a) cellulose triacetate, (b) synthetic polyamides or polyurethanesand (c) polypropylene fibres, except that the thermosol treatment wascarried out at ZOO-220 C. for (a), at 170-200 C. for (b) and at 150 C.for (c).

Equivalent dyeings were also obtained if the 990 parts oftetrachlorethylene were replaced by the same amount of one of thefollowing solvents: methylene chloride, chloroform, carbontetrachloride, dichlorethane, trichlorethane, trichlorethylene,tetrachlorethane, dichloropropane, 1,1,1-trichloropropane, chlorobutane,dichlorobutane, perfiuoro-n-hexane, l,2,2-trifiuorotrichlorethane and1,1,1-trifiuoropentachloropropane.

The dyestuff used had been manufactured as follows: 5 parts of1-amino-2,4-dihydroxy-anthraquinone were warmed for one hour to 200 C.together with 2.5 parts of anhydrous sodium carbonate and 6 parts ofn-hexadecanol-p-tosyl ester in 50 parts of anhydrous nitrobenzene. Thereaction mixture, cooled to 80 C., was mixed with 80 parts of methanoland 5 parts of glacial acetic acid and after standing for several hoursthe product was filtered off in the cold. After washing with methanoland water, 8.2 parts of the abovementioned dyestufi were obtained,melting point after recrystallisation from pyridine: 101-10 2 C.

EXAMPLE 2 A knitted fabric of polyhexamethylenediamine adipate filamentsis impregnated at room temperature with a clear red solution whichcontains 10 parts of 1-amino-2-decanoxy-4-hydroxyanthraquinone and 7parts of nonylphenolheptaglycol-ether in 983 parts oftetrachlorethylene. After squeezing out to a weight increase of 60%, theknitted fabric is dried for one minute at 80 C. Thereafter the dyestuflfis fixed by heating the knitted fabric to 192 C.

, for 45 seconds. Small amounts of non-fixed dyestuff are then eluted bybrief treatment in cold tetrachlorethylene. After drying, a clear reddyeing is obtained, which is distinguished by its high dyestuif yield,very good build-up and very good fastness properties, especially verygood fastness to thermofixing, washing, rubbing and light.

An equivalent clear red dyeing was obtained analogously on woven fabricsof anionically modified polyhexamethylenediamine adipate. An equivalentdyeing was also obtained if instead of the 983 parts oftetrachlorethylene the same amount of toluene, xylene, chlorobenzene,dichlorobenzene or 1,2,2-trifluoro-trichloethane was used.

The dyestuff used had been manufactured as follows: 80 parts of decanoland 25 parts of dimethylformamide together with 9 parts of powderedpotassium hydroxide were warmed to C. After the introduction of 20partsof 1-amino-2-phenoxy-4-hydroxy-anthraquinone the reactlon mixturewas stirred at 150 C. until the starting material had completely reactedand was then cooled and mixed with 50 parts of methanol. The dyestuffwhich separated out was filtered off and washed with methanol and water.Yield: 18.5 parts.

EXAMPLE 3 A woven fabric of polypropylene fibres is impregnated at roomtemperature with a clear red solution which contains parts of1-amino-2-(1-methyl-2-[p-cyclohexylphenoxy]-ethoxy)-4-hydroxy-anthraquinoneand 7 parts of nonylphenol-heptaglycolether in 983 parts oftetrachlorethylene. After squeezing out to a weight increase of 60%, thewoven fabric is dried for one minute at 80 C. Thereafter the dyestuif isfixed by heating the woven fabric to 140 C. for 30 seconds. Non-fixedamounts of dyestuff are eluted by brief treatment in cold solvent. Aclear red dyeing is obtained, which is distinguished by high dyestuifyield, very good build-up and excellent fastness properties, especiallyvery good fastness to thermofixing, washing, rubbing and light.

The dyestuff used had been manufactured as follows: 80 parts ofl-(p-cyclohexyl-phenoxy)-propanol-2, 2 parts of powdered potassiumhydroxide and 10 parts of l-amino- 2-phenoxy-4-hydroxy-anthraquinonetogether with 30 parts of N-methylpyrrolidone were heated to 130140 C.for 8 hours. After the addition of 100 parts of methanol, 10 parts ofWater and 2 parts of glacial acetic acid to the cooled reaction mixture,the dyestuif which separated out was filtered oflf and washed withmethanol and Water. Yield: 11.3 parts, melting point afterrecrystallisation from pyridine: 204-205 C.

EXAMPLE 4 A woven fabric of poly-l,4-cyclohexanedimethyleneterephthalate is impregnated at room temperature with a clear redsolution which contains 10 parts of 1-amino-2-[2-(2'-butoxyethoxy)-ethoxy] -4-hydroxy anthraquinone and 7 parts ofnonylphenol-heptaglycol-ether in 983 parts of tetrachloroethylene. Aftersqueezing out to a weight increase of 60%, the woven fabric is dried forone minute at 80 C. Thereafter the dyestuff is fixed by heating thewoven fabric to 190-220 C. for 45 seconds. The small amount of non-fixeddyestuff is then eluted by brief treatment in cold tetrachlorethylene.After drying, a clear red dyeing is obtained, which is distinguished byits high dyestuif yield, very good build-up and excellent fastnessproperties, especially very good fastness to thermofixing, washing,rubbing and light.

A clear red dyeing was obtained analogously on a woven fabric ofanionically modified polyethylene terephthalate filaments.

The dyestuif used had been manufactured as follows: parts of1-amino-2-phenoxy 4 hydroxy anthraquinone were introduced at 130 C. intoa mixture of 60 parts of diethylene glycol monobutyl ether and 2 partsof powdered potassium hydroxide. The reaction is complete after 4 hours.The resulting dyestuif was separated out of the reaction mixture byadding 80 parts of water. After filtering and washing with methanol andwater, 16.2 parts of dyestuff were obtained. Melting point afterrecrystallisation from pyridine: 92 C.

EXAMPLE 5 A woven fabric of polyethylene terephthalate fibres isimpregnated at room temperature with a clear red solution which contains10 parts of l-amino-2-[2-(1,3-bis-p-tert.- butylphenoxy) -isopropoxy]-4-hydroxy-anthraquinone and 7 parts of nonylphenol-heptaglycol-ether in982 parts of tetrachlorethylene. After squeezing out to a weightincrease of 60%, the woven fabric is dried for one minute at 80 C.Thereafter the dyestutf is fixed by heating the woven fabric to 190-220C. for 45 seconds. The small amount of non-fixed dyestuif is then elutedby brief rinsing with cold tetrachlorethylene. After drying, a clear reddyeing is obtained, which is distinguished by its high dyestuif yield,very good build-up and excellent fastness prop erties, especially verygood fastness to thermofixing, Washing, rubbing and light.

The dyestuif used had been manufactured as follows: 50 parts ofu,a-glycerine-di-(p-tert.-butyl)-phenyl-ether, 15 parts ofN-methylpyrrolidone, 2 parts of potassium hydroxide and 10 parts ofl-amino-2-methoxy-4-hydroxyanthraquinone were heated to 130 C. for 5hours. After adding parts of methanol and 2 parts of glacial acetic acidto the cooled reaction mixture, the dyestutf which separated out wasfiltered off and washed with methanol and water. Yield: 14.3 parts,melting point after recrystallisation from pyridine: 132-133 C.

EXAMPLE 6 A woven fabric of polyethylene terephthalate fibres isimpregnated at room temperature with a clear red solution which contains10 parts of l-amino-Z-[y-benzyloxypropoxy]-4-hydroxy-anthraquinone in990 parts of 1,1,1- trichlorethane. After squeezing out to a weightincrease of 60%, the dyestuif is fixed by treating the woven fabric withsuperheated 1,1,l-trichlorethane vapour at 140 C. for 45 seconds.Thereafter the small amount of non-fixed dyestuff is eluted by briefrinsing in cold 1,1,1-trichloethane. After drying, a clear red dyeing isobtained, which is distinguished by its high dyestuff yield, very goodbuildup and good fastness properties.

The dyestuif used had been manufactured as follows: 60 parts ofpropanediol l-,3monobenzl-ether together with 2 parts of powderedpotassium hydroxide and 10 parts of 1-amino-2-phenoxy 4 hydroxyanthraquinone were warmed to l40 C. until the starting material hadcompletely reacted. After the usual working up, 9.8 parts of dyestuifwere obtained, melting point after recrystallisation from pyridine: -14lC.

EXAMPLE 7 A woven fabric of poly-l,4-cyclohexanedimethyleneterephthalate is impregated at room temperature with a clear redsolution which contains 10 parts of 1-amino-2- (2-[2'isopropyl-3'-methyl-phenoxy]-ethoxy)-4-hydroxyanthraquinone in 990 partsof tetrachlorethylene. After squeezing out to a weight increase of 60%,the dyestufl is fixed by treating the woven fabric with superheatedtetrachlorethylene vapour at C. for 35 seconds. Thereafter the smallamount of non-fixed dyestuff is eluted by brief rinsing in coldtetrachlorethylene. After drying, a clear red dyeing is obtained, whichis distinguished by its high dyestuif yield, very good build-up andexcellent fastness properties.

The dyestuff used had been manufactured as described in Example 4,except that instead of the 60 parts of diethylene glycol monobutylether, 60 parts of ethylene glycol mono-(2-isopropyl-3-methyl)-phenylether were employed.

EXAMPLE 8 A woven fabric of polyethylene terephthalate fibres isimpregnated at room temperature with a clear red solution which contains10 parts of l-amino-Z-n-dodecylmercapto-4-hydroxy-anthraquinone and 7parts of nonylphenyl-heptaglycol-ether in 983 parts oftetrachlorethylene. After squeezing out to a weight increase of 60%, thewoven fabric is dried for one minute at 80 C. and the dyestuff is fixedby heating the woven fabric to 220 C. for one minute. A clear,bluish-tinged red dyeing is obtained which is distinguished by highdyestuff yield, very good build-up and good fastness properties,especially good fastness to thermofixing, washing, rubbing and light.

The dyestuff used had been manufactured as follows: 12 parts of1-amino-2-bromo-4-hydroxy-anthraquinone were dissolved in 200 parts ofpyridine. The solution was mixed with 4 parts of powdered potassiumhydroxide and then with 25 parts of n-dodecylmercaptan, and weresubsequently warmed to 40-50 C. The dyestuif formed was separated out ofthe reaction mixture by adding 200 parts of methanol and 5 parts ofglacial acetic acid, filtered otf and washed with methanol and water.Yield: 16.2 parts.

Clear red to bluish-tinged red dyeirlgs of excellent fastness propertieson woven fabrics of polyester, triacetate, polyamide, polyurethane andpolyolefin fibres were also obtained if instead of the indicateddyestuff the same amount of one of the dyestuffs indicated in the tablewhich follows, or mixtures of these with one another, were used:

Example Dyestuff 1-amino-2-n-butoxy-4hydroxy-anthraquinone.l-amino-Z-(lanethyl-propoxy)4hydroxy-anthraquinoue.1-arnino-2-[2-(2-methyl)-pr0poxy]-4-hydroxy-anthraquinone.l-amino-Z-(Z-methyl-propoxy)-4-hydroxy-anthraquinoue.1-amino-2-n-pentoxy 4 hydroxy-anthraquinone.Lamina-2-(3-methyl-butoxy)-4-hydroxy-anthraquinone.l-amino-2-nhexoxyl-hydroxy-anthraquinone.1-amino-2-(1,3-bis-methyl-but0xy)-4-hydroxyanthraquinone.1-amino-2-(2,2-bis-methyl-butoxy)4-hydroxy-anthraquinone.l-amino-Z-(Z-ethyl-butoxy)-4-hydroxy-anthraquinone.1-aminoZ-n-heptoxy-4-hydroxy-anthraquinonc.l-amino-Z-n-octyloxy-4-hydroxy-anthraquinone.l-amino-Z-(Z-ethyl-hexoxy)-4hydroxy-anthraquinone.Lamina-2-(2,2bis-methyl-hexoxy)-4-hydroxy-anthraquinone.l-amino-Z-(2,2-bis-methyloetyloxy)4-hydroxy-antl1raquinone.1-arnino-2-n-dodecanoxyt-hydroxy-anthraquinone.l-arnino-Z-(2,2-bis-metl1yl-deean0xy)-4-hydroxy-anthraquinone.l-amino-2-u-tetradecauoxyi-hydroxy-anthraquiuone:l-amino-Z-n-oetadecanoxy 4-hydroxy-anthraquinone.l-amino-2-u-butylmercapto-4-hydroxy-anthraqninone.l-amino-Z-n-pentylmercapto t-hydroxy-anthraquinone.l-amino-2-n-hexylmereapto-4-l1ydr0xy-anthraquiuone.l-amino-3-butylrnercapto-et-hydroxy-anthraquinone.1-ainin0-3-n-dodecylmereapto-4-hydroxy-anthraquinone.1-amino-2(2-isopropoxy-ethoxy)4-hyclroxy-anthraquinone. Lamina-2-(2n-butoxy ethoxy)-4-hydroxy-antln'aquinone.l-amino-2-[2-(2-ethyl-hexoxy)-eth0xy]-4-hydroxy-anthraquinonel-amino-Z-[Z-(T-(Wethylhexoxy)-ethoxy)ethoxy1-4-hydroxyanthraqmnone.l-amino-2-(3-methoxy-butoxy) -4hy 1roxy-anthraquinone.l-amino-2-(l-methyl-Z-phenoxy-ethoxy)-4-hydroxy-anthraquinone.1-amino-2-( 1-methyl-2-[4 -benzylphenoxy]-ethoxy)-4-hydroxyanthraquinone.l-amino-2-(l-ethyLZ-phenoxy-ethoxy)-441ydroxy-anthrauinone. 1-zmino-2-(Z-[ tisooetyl-phenoxy]-ethoxy)4-hydroxy-anthraquinone.1-anu'no-2-(2-[2-cyelohexyl-phenoxy]ethoxy)-4-l1ydroxyanthraquinone.1-amino-2-(2-[2-tert.-butyl-phenoxy]ethoxy)4-hydroxyauthraquinone.1-amino-2- (2-[4-(a,a dimethylbenzyl) -phenoxy]-ethoxy) -4hydroxy-anthraquinone.1-arm'no'2-(2-[2-sec.-butylphenoxy]-ethoxy)-4hydroxyauthraquinone.

46 1-amino-2(2-[2-isopropyl-5-methyl-phenoxy]-ethoxy)-4-hydroxy-anthraquinone.

47 1amino-2-(2-[4-butoxycarbonyl-phenoxy]-ethoxy)-4-hydroxy-anthraquinone.

48 1-arnino-2-(2-[4-amyloxycarbonyl-phenoxy]-ethoxy)4-hydroxy-antln'aquinone.

49l-amino-Z-(2-[2-isopropyl-B-methylphenoxy]-ethylmereapto)-4-hydroxy-anthraquinone.

60 1-amin0-3-(2,Z-bis-methyl-oetyloxy)-4-hydroxy-anthraquinone.

51 1-amino-3-(2-n-butoxy-ethoxy)-4-hyd1oxy-anthraqumone.

52 .2 l-amino-Ii-(l-methyl-2-[4-cyelohexylphenoxy1-ethoxy)-4-hydroxyanthraquinone.

53 1-amino-3-(2-[2-isorpropyl-3-methyl-phenoxyl-ethoxy)-4-hydroxy-anthraquinone.

54 1-amino-2-(leyelohexoxyethoxy)-4-hydroxy-anthraqu1none.

55- 1-amino-.-(Z-benzyloxyethoxy)-4-hydroxy-anthraquinone.

56 l-amino-2-(2-[4-methylbenzyloxy]-ethoxy)-4-hydroxyanthraquinone.

57 l-amino-2-(3-[4-cyclohexylphenoxy]-propoxy) +hydroxyanthraquinone.

58 1-a1nino-2-(2-[4-methyl-3-isopropylflehlorophenoxy]-ethoxy)-4-hydr0xy-anthraquinone.

59 1-amino-2-(2-[1,3-bis-p-eyelohexylphenoxy]-isopropoxy)-4-hydroxy-anthraquinone.

60 l-amino-z(1H1,3-bis-n-butoxy]-isopropoxy)4-hyd.roxyanthraquinone.

61 l-amiuo-Z-(Z-[l,3-bls-cyclohexxy]-isopropoxy)-4-hydroxyanthraquinone.

62 l-nmino-Z-(2-[1p'cyclohexylphenoxy-3-phenoxy]-isopropoxy)-4-hydroxy-anthraqninone.

63l-amino-Z-(2-[1-p-methylmercaptophenoxy-3-p-benzylphenoxy]-isopropoxy)-4-hydroxy-anthraquinone.

64= l-amino-Z-(2-[l-p-rnethylphcnoxy-3-phenoxy]-isopropoxy)-4-hydroxy-anthraquinone.

65 l-amino-Z-(2*[1-p-methylphenoxy-3-o-eltloropheuoxy]-isopropoxy)-4-hydroxyanthraquinone.

66 l-amino-Z-n-octylmercapto-4=-l1ydroxy-antluaquinono.

67 l-amino-2rtert.octyhnercapto-4-hydroxy-anthraqurnone.

68 l-ami110 2-tert.deeylmercapto-l-hydroxy-anthraqulnone.

69 l-amino-mhexadecylmei'capto4hyd1'0xy-anthraqulnone.

70 l-amino-2-n-cetadecylmcreapto4-hydroxy-anthraqmnone.

8 EXAMPLE 71 A woven fabric of cellulose triacetate fibres isimpregnated at room temperature with a clear red solution which contains10 parts of a dyestuif mixture of 5 parts of 1- amino3-octadecanoxy-4-hydroxy-anthraquinone and 5 parts of 1 amino3-hexadecanoxy-4-hydroxy-anthraquinone which had been manufactured inthe manner indicated below, and 7 parts of nonylphenol-heptaglycoL etherin 983 parts of tetrachlorethylene. After squeezing out to a weightincrease of 60%, the woven fabric is dried for one minute at C.Thereafter the dyestuif is fixed by heating the woven fabric to 215 C.for one minute. A clear red dyeing is obtained, which is distinguishedby high dyestnfi yield, good buildup and good fastness properties,especially good fastness to thermofixing, washing, rubbing and light.

The dyestuff mixture used had been manufactured-as follows: 20 parts of1,2-dihydroxy-4-p-tosylamino-anthraquinone in parts of anhydrousnitrobenzene were heated together with 6 parts of sodium carbonate, 10parts of n-0ctadecan0l-p-tosyl ester and 10 parts ofnhexadecanol-p-tosyl ester to 200 C. for 1 /2 hours. The dyestulfmixture was separated out by adding 200 parts of methanol and 8 parts ofglacial acetic acid to the cooled reaction batch and was subsequentlyfiltered off and washed with methanol and water. Yield: 26.8 parts of a1:1 dyestuff mixture of 1-hydroxy-2-octadecanoxyand 1hydroxy-2-hexadecanoxy-4-p-tosylamino-anthraqu1none.

18 parts of this dyestuff mixture were dissolved in 100 parts ofconcentrated sulphuric acid and the solution was stirred for one hour atl5-20 C. After working up the solution with water, 13 parts of a 1:1dyestuff mixture of 1-arnino-3-octadecanoxy-and 1-amino-3-hexadecanoxy-4-hydroxy-anthraquinone were obtained.

We claim:

1. Process for the continuous dyeing of synthetic polyester fibermaterial comprising the steps of (A) impregnating the fiber materialwith a non-aqueous dyeing liquor said liquid consisting essentially ofan organic solvent and an anthraquinone dyestuff; said organic solventconsisting of water-immiscible halogenated hydrocarbon having a boilingpoint of 40 C. to C.; said anthraquinone dyestufi having the formula 2.The process of claim 1 in which the anthraquinone dyestuif has theformula I OH in which X is oxygen or sulfur; and R is C C -alky1.

9 3. The process of claim 1 in which the anthraquinone dyestulf has theformula in which n is 1 or 2; and R is C C -alkyl, cycloalkyl, aralkyl,phenyl or phenyl substituted with C -C -alkyl, cycloalkyl, aralkyl, C -C-alkoXy, C -C -alkylmercapto, C -C -alkoxycarbonyl or chlorine; with theproviso that the sum of the carbon atoms in R is 2 to 18.

4. The process of claim 1 in which the anthraquinone dyestufi has theformula in which R, and R independently of one another are C -C -alkyl,cycloalkyl, aralkyl, phenyl, or phenyl substituted with C -C -alkyl,cycloalkyl, aralkyl, C -C alkoxy, C -C -alkylmercapto, C -Calk0xycarbonyl or chlorine; with the proviso that the sum of the carbonatoms in R and R is 4 to 36.

6. The process of claim 1 in which the anthraquinone dyestuif is 1amino-2-[2-(2'-but0xyethoxy)-eth0Xy]-4- hydroxy-anthraquinone.

7. The process of claim 1 in which the anthraquinone dyestuff is1-amino-2- [-(2'-isopropyl-3'-methyl-phenoxy)- ethoxy]-4-hydroxy-anthraquinone.

8. The process of claim 1 in which the anthraquinone dyestutf is 1 amino2-(Z-n-butoxyethoxy)-4-hydroxyanthraquinone.

9. The process of claim 1 in which the anthraquinone dyestuff is1-amino-2-[2-(2'-sec.-butylphenoxy) ethoxy] -4- hydroXy-anthraquinone. I

10. The process of claim 1 in which said anthraquinone dyestuff issoluble in said water-immiscible organic solvent.

11. The process of claim 10 in which the dyed material is subjected to asubsequent step of (C) rinsing with cold water-immiscible organicsolvent in which said anthraquinone 'dyestuff is soluble.

12. The process of claim 1 in which said water-immiscible organicsolvent is an aliphatic chlorohydrocarbon having a boiling point ofbetween 40 and C.

13. The process of claim 1 in which said water-immiscible organicsolvent is selected from the group consisting of tetrachloroethylene,trichloroethylene, 1,1,1-trichloroethane, 1,1,1,-trichlor0propane andmixtures thereof.

References Cited UNITED STATES PATENTS 2,828,180 3/1958 Sertorio 8-623,264,325 8/1966 Lewis 260-380 3,510,243 5/1970 Sueret et al. 8-3

FOREIGN PATENTS 1,045,839 10/ 1966 Great Britain.

1,002,876 9/ 1965 Great Britain 8-39 603,298 8/ 1960 Canada 260-3801,217,380 12/ 1970 Great Britain.

GEORGE F. LESMES, Primary Examiner P. IVES, Assistant Examiner U.S. C1.X.R. 825; 260-380

